WO2014136073A1 - Composites d'aérogel d'oxyde de titane - Google Patents

Composites d'aérogel d'oxyde de titane Download PDF

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WO2014136073A1
WO2014136073A1 PCT/IB2014/059485 IB2014059485W WO2014136073A1 WO 2014136073 A1 WO2014136073 A1 WO 2014136073A1 IB 2014059485 W IB2014059485 W IB 2014059485W WO 2014136073 A1 WO2014136073 A1 WO 2014136073A1
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aerogel
titanium oxide
porosity
previous
anyone
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PCT/IB2014/059485
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Endre HORVÁTH
Laszlo Forro
Arnaud Magrez
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Ecole Polytechnique Federale De Lausanne (Epfl)
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Priority to EP14718744.7A priority Critical patent/EP2964577B1/fr
Priority to US14/773,431 priority patent/US10569248B2/en
Publication of WO2014136073A1 publication Critical patent/WO2014136073A1/fr

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Definitions

  • the invention relates to titanium oxide aerogels, in particular to titanium oxide binary or ternary (e.g. titanium oxide-carbon) aerogel monoliths possessing ordered meso- and macroporosity.
  • Prior art Aerogels are unique among solid materials. They have interesting physical and chemical properties e.g. very low skeletal densities (up to 95% of their volume is air), large open porosity, high optical transparency and high specific surface area associated with extremely low sound velocity and thermal conductivity. Formation of the highly porous three-dimensional network in particular the kind of precursors and the reaction conditions are the key steps in the preparation of aerogels. The resulted micro, meso -and macroporosity is highly influenced by the physico-chemical processing used during the preparation. In the beginning sponge-like solid network is filled with liquid. In most of the cases special drying techniques must be applied to exchange the pore liquid with air while maintaining the filigrane solid network. Basically all metal or semimetal oxides are known to form gels, and many applied for the fabrication of aerogels.
  • TiCh aerogels were prepared by Teichner et al. in 1976. 1 Until today, titanium-propoxide, -butoxide and -sulfate are primarily used as precursors. 2 " 6 TiCh aerogels can be prepared completely amorphous or with a network of crystalline anatase primary particles. 7"9 The porosity of the reported TiCh aerogels is typically 78-90 %. 10 The preparation of aerogels with porosity above 90 % is a real technological challenge. According to our knowledge such a porous aerogels from pure titanium oxide have not been realized yet. The closest article to our invention is that of published by Tian and coworkers in 2006.
  • the primary object of the present invention is to provide a titanium oxide aerogel or a titanium oxide based binary or ternary (e.g. titanium oxide-carbon) aerogel monolith possessing extremely high porosity.
  • the invention therefore relates to products, processes, methods and uses as defined in the claims.
  • the viscosity of the aerogel before the drying process is preferably 80-100 Pa/s.
  • the aerogel advantageously has a specific surface area greater than 60 m 2 /g and porosity larger than 60 %. Preferably the surface area ranges from 60 to 300 m 2 /g.
  • the obtained porosity can be very high, typically up to 99.6 %.
  • the aerogel has an extremely open and continuous pore structure preferably containing at least 10 % of slit shaped mesopores (2- 100 nm).
  • the macroporosity (pore diameter larger than 100 nm) can reach 90 %. No unconnected porosity is present in the gel.
  • the porosity can be controlled between 1- 99.6 % by compressing the monolith with a press, rollers etc. (Fig.2-3)
  • the aerogel can be irreversibly compressed up to 99.6 % to its volume.
  • the size of the titanium oxide crystallites in the gel are between 5 nm and 100 nm.
  • the crystallites assemble into elongated particles of several micrometers in length.
  • the aerogel composed of 100 % titanium oxide and shows a white color.
  • the resistivity of the aerogel is higher than 10 13 Ohm*cm.
  • the resistivity of the aerogel can be lowered to 206 Ohm*cm by a thermal treatment at no less than 600 °C under H 2 atmosphere. Depending on the temperature and the duration of the treatment the aerogel shows from light blue to black color.
  • Thermal conductivity of the aerogel is 0.033 W/mK.
  • the composite (binary or ternary) aerogel contains at least 1 % carbon in the form of (carbon nanotubes, carbon nanofibers, carbon microfibers, exfoliated graphene, natural fibers e.g. cellulose fibers, polymer fibers, metallic and metal oxide nano and microfibers etc.) and at least 1 % of metal or metal oxide nanoparticles (Ag, Au, ZrCh, VO2, MnCh etc.).
  • the porous scaffold contains at least 1 % binders and/or surfactants.
  • the resistivity of the carbon nanotube titanium oxide aerogel decreases by ten orders of magnitude (from 10 13 to 10 3 Ohm*cm) between 0 w% and 10 w% carbon nanotube content.
  • the titanium oxide aerogel adsorbs the hydrophilic compounds, however the composite aerogel adsorbs both the hydrophilic and hydrophobic hazardous compounds (molecules, germs). Exposing the aerogel or composite aerogel to UV or visible light different reactive oxygen species (ROS) form.
  • the composite aerogel is twice as active as the highly optimized commercial Degussa P25 in methyl orange photo-decomposition (Fig.7).
  • the E. coli inactivation rate is significantly higher on the surface of the nanocomposite aerogel as compared to the control (Teflon) surface (see Fig. 8). The visible and infrared light heats up the aerogel composite.
  • the aerogel can have a predeterminable shape. It can be shaped in a mold having a shape of a cylinder, cube, sheet or sphere.
  • the aerogel can be also transformed into a supported or self-standing film with a thickness.
  • a surface structured tool is used to apply the pressure, micron and nano sized features (replica of the pressing tool) are created on the surface of the aerogel.
  • Such replicas possess special optical properties permitting applications as a colorful optical grating (Fig. 3 (31, 34)), a Bragg reflector or an antireflective coating.
  • the surface patterning of the aerogel dramatically affects its wetting properties, enabling therefore the making of water repellent (superhydrophobic Fig3(34)) or superhydrophylic surfaces (Fig3(33)).
  • Another object of the present invention is to provide a cheap, simple and easily scalable to m 3 volume method and device for producing titanium oxide based binary, ternary aerogels with extremely high (above 90 %) porosity.
  • the device comprises of a heatable base resistive vessel (PTFE, PP, PA etc. or metallic vessel with internal polymer coating) having a heat insulation layer around the vessel.
  • the mixing paddle or paddles with brush-like end enter into the reaction vessel trough a jacketed condenser from base resistive material attached to the vessel cover.
  • the external mixer allows safe and turbulent mixing of the highly basic mixture with 300-2500 rpm (high shear mixing) at atmospheric pressure.
  • the device is able to operate from room temperature up to 250 °C. With this device titanium oxide composite aerogels can be produced at as low as 80 °C.
  • Another object of the present invention is the use of the titanium oxide aerogels and titanium oxide binary or ternary (e.g. titanium oxide-carbon) aerogel monoliths possessing ordered meso- and macroporosity.
  • the material can be used as a self-cleaning filter e.g. in a solar-thermal water and air purification system, in mesoscopic solar cells e.g. dye sensitized solar cells and perovskite based meso-superstructured solar cells, multifuctional filler in ceramics, metal and polymer composites, thermoelectric material to convert (waste) heat into electricity, heat insulation material and electrode material in lithium ion batteries and supercapacitors.
  • Preferred embodiment Process for fabricating titanium oxide composites comprising the following steps:
  • a titanium containing compound with at least 10 % Ti content in the case of binary, ternary aerogel addition of the second and third compound
  • a base resistive vessel PTFE, PP, PA etc. or metallic vessel with internal polymer coating
  • titanium containing compound is heat-treated at 350-900 °C in (air, O2, H2, Ar, N2 or a mixture of these)
  • titanium containing compound stands for:
  • Ti0 2 anatase, rutile, brookite, Ti02 (B), ⁇ 2 (H), and Ti02 (R))
  • Protonated titanates orthotitanates, metatitanatres e. g. tbTisC )
  • the titanium containing starting material includes from 0.1 to 30% by volume of fibers (carbon nanotubes, carbon nanofibers, carbon microfibers, exfoliated graphene, cellulose fibers, metal or metal oxide nano and microfibers etc.)
  • the porosity and pore size distribution of the gel can be controlled by the rotation speed and temperature (swirling flaw enhanced mixing)
  • the textural properties can be more precisely controlled by including ramps in the temperature, time and turbulent mixing (rpm)
  • alkali metals, alkaline earth metals, inner transition metal, transition metal, post-transition metal c. or saturated salt solution of alkali metals, alkaline earth metals, inner transition metal, transition metal, post-transition metal; Orthotitanates ( ⁇ 2 ⁇ 04, where M is divalent ion) or metatitanates (MTi03, where again M is divalent) aerogels can be synthesized by the subsequent heat treatment (150-1000 °C) of the aerogel embedded into the M salt
  • the gel can be shaped in a mold having a shape of a cylinder, cube, sheet, sphere or supported film or mesh with a thickness (Fig.2)
  • the supported film can be prepared by doctor blading, screen printing, filtering, dip coating, spin coating with a thickness less than 2 micron;
  • the supported film can be removed from the support when the support is a hydrophobic material (PTFE, PA, FTO,ITO etc.)
  • PTFE polymethyl methacrylate
  • PA polystyrene
  • FTO fluoride
  • ITO indium tin oxide
  • the aerogel monolith has the porosity 60-99.6 %
  • the porosity (hence the optical and electronic properties) can be controlled between 1-99.6 % by compressing the monolith with a press, rollers etc. (Fig.2)
  • the transport- and density-dependent properties of the composite aerogel can be tuned by varying the volume fraction of the reactants, thereby increasing the design flexibility of these micro, meso- and macroporous materials for optical, chemical, thermal, magnetic, and electronic applications.
  • the chemical and physical properties of the composite material can be further engineered at multiple points during the processing by modifying porosity, pore size and pore orientation distribution, flexibility and transparency of host solid composite gel, or the composite aerogel.
  • Example Manufacturing process for titanium oxide aerogel composites and their use for the inactivation of harmful chemical and biological agents: with focus on solar-thermal water and air purification
  • the efficient utilization of the energy of visible light (solar energy) is one of the most pressing task for centuries and researchers.
  • Engineered pore structured micro and mesoporous materials e.g. aerogels
  • the present invention can be applied in the field of biological, chemical and particulate filters; more specifically, in the field of photo-catalytic biological, chemical and particulate filters.
  • the present invention provide a device based on a filter that couple the classical filtration separation technology with light induced self-cleaning abilities: increasing its catalytic activity and reducing the potential membrane fouling.
  • First the waterborne and airborne pathological compounds (viruses and bacteria), as well as other organic compounds were separated from the environment (liquid or gas, see Fig.9(91)).
  • the incoming photons heat up the black colored system resulting in a sterilization (pasteurization) effect against biological hazard (Fig4(41)).
  • the present proposal deals with the medium and large scale fabrication of special self- standing titanium oxide aerogel membranes and their binary, ternary composites with ultralong carbon nanotubes/carbon nanowires carbon nanotubes, carbon nanofibers, carbon microfibers, exfoliated graphene, natural fibers as cellulose fibers, polymer fibers etc.(Fig4(41,42)).
  • Fig4(41,42) In order to achieve superior (photo )cataly tic activity, there is the possibility to tailor the inorganic part by doping with metal ions or decorating with different metal or metal oxide nanoparticles Ag, Au, Cu, Fe 2 03, ZrCh, VO2, MnCh etc.(Fig6(61,62,65), Fig8(81,82)).
  • nanocomposite membranes developed from the titanium oxide aerogel disclosed above couple the classical filtration separation technology with self-cleaning abilities: increasing its catalytic activity and reducing the potential membrane fouling.
  • the carbon nanotube content determines the adsorption, as well as the optical, electrical and mechanical properties (see Fig5).
  • the fabrication process allows us to prepare two main membrane architectures.
  • preparation of laminated configuration results in a membrane with alternating layers of the two main constituents (see Fig7(73,74)).
  • the aerogel films in methyl orange decomposition are twice as active as the highly optimized commercial Degussa P25 (Fig8(83)).
  • Escherichia coli bacteria deactivation rate was determined in a flow reactor on UV and VIS irradiated nanocomposite filters. The control experiment in the dark showed no toxicity. In both cases, using the VIS and UV sources, the E. coli inactivation rate was significantly higher on the surface of the nanocomposite aerogel membrane as compared to the control (Teflon) surface (see Fig9(92)).
  • the thickness of the membrane is in the couple of microns or eventually in the submicron regime (see Fig6(64), Fig7). This allows high optical transmittance and low pressure difference operation.
  • This new type of flexible, free-standing aerogel membrane can be easily coupled with conventional HEPA filter technology providing useful additional functionalities. This can be done by:
  • the potential market segments are the indoor air-conditioning in buildings and vehicles (car, airplane industry) and the solar-thermal water purification systems.
  • the Solar-thermal water and air purification system disclosed above is a low cost, durable and easy to operate device which allows producing drinking water from surface water resources at remote places where the construction of water distribution pipelines is not foreseen.
  • Three essential functions are coupled in one device: mechanical filtration, oxidation power and pasteurization.
  • the core element of the Solar-thermal water and air purification system is the photocatalytic titanium oxide based aerogel membrane described above (Fig4-7, Fig 10(130)).
  • One of the main advantages of the device lies in the simple device geometry.
  • the membrane is placed in between two UV-VIS-IR transparent sheets (Fig 10(110,120)) made from polymers, quartz, high purity glass or borosilicate glass.
  • the two sheets have to be sealed (Fig 10(140)) so as to have an entry and an exit hole (Figl0(150,160)).
  • the flux of the liquid or gas can be controlled by pressure and/or tilting angle of the device. In principle the device does not require any electricity. In order to function it requires gravitational force (which is abundant) and a light source (natural or artificial). When the upper reservoir is filled with the contaminated water the gravitational and capillary forces will allow only the liquid and particles smaller than 10 nm to enter into the porous aerogel membrane (Figl0(130)). The organic compounds will slowly diffuse through the porous aerogel membrane. When exposed to light the photochemical reactions will kill or inactivate the hazardous biological or chemical compounds capable to enter into the porous scaffold.
  • Inactivation can be anything e.g. oxidization, denaturation, pasteurization.
  • the physico-chemical properties of the liquid or gas will be different before entering and after leaving the device (Fig 10(150, 160)). Since the incoming photons heat up the black colored system the device with minor modifications could be used as a solar-thermal collector as well.
  • Multifunctional filler (functionalities: pigment, mechanical reinforcement, bioactivity, bio-inertness, self-cleaning ability, dielectric properties) inorganic composites: ceramics, dielectrics, cement industry. 5) Multifunctional filler (functionalities: purple, blue, green, yellow, orange pigment due to the plasmonic color of the supported plasmonic nanoparticles (unconventional colored alloys of Au, Ag, Cu), mechanical reinforcement, bioactivity, bio-inertness, self-cleaning ability, dielectric properties) in metals: jewellery, watch industry.
  • Thermoelectric material to convert (waste) heat into electricity was as high as 700 ⁇ / ⁇ .
  • Electrode material in supercapacitors High surface area combined with the engineered porosity.

Abstract

L'invention porte sur des aérogels d'oxyde de titane, en particulier sur des monolithes d'aérogels composites binaires ou ternaires d'oxyde de titane (par exemple d'oxyde de titane-carbone) possédant une mésoporosité et une macroporosité ordonnées. L'échafaudage poreux peut être formé avec ou sans ajout de liants et/ou de tensioactifs. L'aérogel obtenu par ce procédé a une surface spécifique supérieure à 60 m2/g et une porosité supérieure à 60 %. La surface spécifique va de 60 à 300 m2/g. La porosité peut être aussi élevée que 99,6 %. La taille des cristaux d'oxyde de titane est comprise entre 5 nm et 100 nm. L'aérogel contient 100 % d'oxyde de titane. L'aérogel composite (binaire ou ternaire) peut être préparé par ajout d'au moins 10 % de carbone sous la forme de nanotubes de carbone, de nanofibres de carbone, de microfibres de carbone, de graphène exfolié, de fibres de cellulose, de fibres de polymère et de nanofibres ou microfibres d'oxyde métallique et de métal, etc. L'aérogel peut être préparé sous une forme prédéterminée. Il peut être mis en forme dans un moule ayant une forme de cylindre, de cube, de feuille ou de sphère. L'aérogel peut également être transformé en un film soutenu ou autoporté ayant une épaisseur. Le matériau peut être utilisé comme filtre autonettoyant, par exemple dans un système thermosolaire de purification d'eau et d'air, dans des photopiles mésoscopiques par exemple des photopiles à colorant, comme charge multifonctionnelle dans des composites de polymère, dans des céramiques, dans des métaux, comme matériau thermoélectrique pour convertir de la chaleur (résiduelle) en électricité, comme matériau isolant thermique et comme matière d'électrode dans des batteries au lithium-ion et des supercondensateurs.
PCT/IB2014/059485 2013-03-06 2014-03-06 Composites d'aérogel d'oxyde de titane WO2014136073A1 (fr)

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